Thiadiazolopyridine polymers, their synthesis and their use

Abstract

The present invention relates to thiadiazolopyridine polymers, their synthesis and their use. The present invention further relates to organic electronic devices comprising such thiadiazolopyridine polymers.

The invention claimed is: 
     
       1. A polymer comprising
 (i) a first monomer unit M 1  of formula (I) in a first molar ratio m 1   
 
       
         
           
           
               
               
           
         
         (ii) a second monomer unit M 2  of formula (II) in a second molar ratio m 2   
       
       
         
           
           
               
               
           
         
         (iii) one or more third monomer units M 3 , each being independently of each other selected from the group consisting of formula (III), formula (IV), formula (V), and formula (VI), in a third molar ratio m 3 , 
       
       
         
           
           
               
               
           
         
         (iv) one or more fourth monomer units M 4 , each independently of the other, selected from one or more electron donors comprising a group selected from the group consisting of aryl, heteroaryl, ethene-2,1-diyl (*—(R 81 )C═C(R 82 )—*) and ethyndiyl (*—C≡C—*), wherein such aryl or heteroaryl group is different from formulae (I) to (VI), in a fourth molar ratio m 4 ;
 and 
 
         (v) a fifth monomer unit M 5  of formula (VII) in a fifth molar ratio m 5 , 
       
       
         
           
           
               
               
           
         
         wherein, independently at each occurrence, one of X 1  and X 2  is N and the other is C—R 71 , and X 3  is at each occurrence independently selected from the group consisting of O, S, Te, Se and N—R 91 , 
         wherein 
         the sum of first molar ratio m 1  and second molar ratio m 2  is at least 0.10 and at most 0.90, 
         the third molar ratio m 3  is at least 0 and at most 0.80, 
         the fourth molar ratio m 4  is at least 0 and at most 0.20, 
         the fifth molar ratio m 5  is at least 0.10 and at most 0.90, and 
         the sum of the molar ratios m 1 +m 2 +m 3 +m 4 +m 5 =1, 
         with the respective molar ratios m 1  to m 5  being relative to the total number of monomer units M 1  to M 5 , and 
         wherein, independently at each occurrence, R 11  to R 14 , R 21  to R 24 , R 31  to R 34 , R 41  to R 43 , R 51  to R 58 , R 61  to R 68 , R 71 , R 81  to R 82  and R 91  are independently of each other H or a carbyl group. 
       
     
     
       2. The polymer according to  claim 1 , wherein at least 50% of the first monomer units M 1  comprised in the polymer are comprised in a first sequence unit S 1 , wherein the first monomer unit M 1  is adjacent to at least one monomer unit of formula (VII). 
     
     
       3. The polymer according to  claim 1 , wherein at least 50% of the second monomer units M 2  comprised in the polymer are comprised in a second sequence unit S 2 , wherein the second monomer unit M 2  is adjacent to at least one monomer unit of formula (VII). 
     
     
       4. The polymer according to  claim 1 , wherein at least 50% of the third monomer units M 3  comprised in the polymer are comprised in a third sequence unit S 3 , wherein the third monomer unit M 3  is adjacent to at least one monomer unit of formula (VII). 
     
     
       5. The polymer according to  claim 1 , wherein at least 50% of the fourth monomer units M 4  comprised in the polymer are comprised in a fourth sequence unit S 4 , wherein the fourth monomer unit M 4  is adjacent to at least one monomer unit of formula (VII). 
     
     
       6. The polymer according to  claim 1 , wherein said polymer comprises a sequence unit S 1  of formula (S-I) 
       
         
           
           
               
               
           
         
       
     
     
       7. The polymer according to  claim 1 , wherein said polymer comprises a second sequence unit S 2  of formula (S-II) 
       
         
           
           
               
               
           
         
       
     
     
       8. The polymer according to  claim 1 , wherein said polymer comprises one or more third sequence units S 3  which are, independently of each other selected from the group consisting of formula (S-III), formula (S-IV), formula (S-V), and formula (S-VI) 
       
         
           
           
               
               
           
         
       
     
     
       9. The polymer according to  claim 1 , wherein said polymer comprises one or more fourth sequence unit S 4  of formula (S-VII) 
       
         
           
           
               
               
           
         
       
       wherein M 4  is at each occurrence independently as defined above. 
     
     
       10. The polymer according to  claim 1 , wherein for m 3 >0 the ratio (m 1 +m 2 )/m 3  is at least 1 and at most 100. 
     
     
       11. The polymer according to  claim 1 , wherein the first molar ratio m 1  is at least 0.10. 
     
     
       12. The polymer according to  claim 1 , wherein if m 1 =0 or m 2 =0 then m 3  is at least 0.10 and at most 0.80. 
     
     
       13. A mixture or a blend comprising one or more polymers of  claim 1  and one or more compounds or polymers selected from the group consisting of binders and compounds or polymers having semiconducting, charge transport, hole transport, electron transport, hole blocking, electron blocking, electrically conducting, photoconducting or light emitting properties. 
     
     
       14. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer of  claim 1 . 
     
     
       15. A component or device comprising the polymer of  claim 1 , said component or device being selected from the group consisting of organic field effect transistors, thin film transistors, integrated circuits, logic circuits, capacitors, radio frequency identification tags, devices or components, organic light emitting diodes, organic light emitting transistors, flat panel displays, backlights of displays, organic photovoltaic devices, organic solar cells, photodiodes, laser diodes, photoconductors, organic photodetectors, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, charge injection layers, charge transport layers or interlayers in polymer light emitting diodes (PLEDs), Schottky diodes, planarizing layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates, conducting patterns, electrode materials in batteries, alignment layers, biosensors, biochips, security markings, security devices, and components or devices for detecting and discriminating DNA sequences. 
     
     
       16. A component or device according to  claim 15 , wherein said component or device is an organic photodetector. 
     
     
       17. The polymer according to  claim 1 , wherein said polymer contains at least 50 wt % of monomer units M 1  to M 5 . 
     
     
       18. The polymer according to  claim 1 , wherein m 1 =0 or m 2 =0 and m 3  is at least 0.10 and at most 0.80. 
     
     
       19. The polymer according to  claim 1 , wherein m 4  is at least 0.01. 
     
     
       20. The polymer according to  claim 1 , wherein m 5  is at least 0.15 and at most 0.85. 
     
     
       21. The polymer according to  claim 1 , wherein m 3 >0 and the ratio (m 1 +m 2 )/m 3  is at least 1 and at most 100. 
     
     
       22. The polymer according to  claim 1 , wherein the polymer has a molecular weight M n  of at least 5,000 g/mol and at most 250,000 g/mol. 
     
     
       23. The polymer according to  claim 1 , wherein said polymer does not contain monomer units of optionally substituted benzo[1,2-b;4,5-b′]dithiophene.